MIXTURES OF POLYAMINO ACIDS AND CITRATE

Abstract: Polyamino acids or their salts mixed with citric acid or its salts, in a ratio of 75:25 to 0.1:99.9, polyamino acid or its salt to citric acid or its salts, and especially in a ratio of 1:1 to 1:99 polyamino acids or their salts to citric acid or its salts, provide a much higher rate of chelation of calcium ion than expected on the basis of the addition of the polyamino acid to citric acid. Such mixtures may be used in high volume water applications such as boiler, cooling, oil well, agricultural sprays and irragation water. They are also useful in preventing scale formation on fabrics when formulated with laundry detergents and in preventing scale formation on glassware when formulated in dishwashing detergents.

Description: MIXTURES OF POLYAMINO ACIDS AND CmiATE FIELD OF THE INVENTION This invention relates to the use of mixtures polyamino acids and citric acid or their salts to provide a synergistically enhanced calcium chelating mixture. DESCRIPTION OF RELATED ART U.S. Pat. 3,474,083 discloses a method for making copolypeptides by heating to L-lysine and L-glutamic acid or L-aspartic acid in a oil bath at 80° to 160° C in an aqueous medium for two to four hours. U.S. Pat.3,846,380 discloses the preparation and composition of copolymers of polyamino acids with primary or secondary aliphatic amines, followed by alkaline hydrolysis to provide surface active agents. Emphasis is placed on long chain alkylamines having eight to twenty carbon atoms. The products formed are said to have good solubilizing ability, emulsifying and dispersing properties, as well as good foaming properties. They are useful as foaming agents, solubilizing agents, dispersing agents, emulsifying agents, rust-proofing agents, fiber-treating agents, level dyeing agents and retarding agents. U.S. Pat. 4,363,797 discloses the use of polyaspartic acid derivatives for use in cosmetic compositions. Ger. Offen. DE 3,724,460 discloses the use of surfactant compositions with skin mildness which contain polyglutamic or polyaspartic acid and their salts. U.S. Pat. 4,534,881 discloses the use of polyaspartate and polyaspartate copolymers to inhibit CaC0 3 formation. U.S. Pat. 4,696,981 discloses a method for making polyamino acids with miέrowaves and a method of heating to make copolyamino acids in a oil bath at 180° for four hours to achieve maximum yields. U.S. Pat. 4,839,461 discloses a method for making polyaspartic acid from maleic acid and ammonia which is useful in preventing scale on glassware in automatic dishwasher formulations. U.S. Pat 5,057,597 discloses a method for the polycondensation of aspartic acid to produce polyaspartic acid by heating the aspartic acid in a fluidized bed reactor to 221° C. for a period of 3-6 hours in a nitrogen atmosphere followed by conventional alkaline hydrolysis. U.S. Pat 5,116,513 discloses the use of polyaspartic acid as an inhibitor of calcium sulfate and barium sulfate precipitation. U.S. Pat 5,152,902 discloses the use of polyaspartic acid as an inhibitor of calcium carbonate and calcium phosphate precipitation. European Patent Application 0 454 126 Al discloses the use of polyamino acids as builders in detergent formulations. European Patent Application 0 511 037 Al discloses the use of polyimide biopolymer, especially those from aspartic and glutamic acids as dispersants in detergent formulations. U.S. Pat. Application 07/926,242, filed August 7, 1992, by Louis L. Wood, incorporated herein by reference, discloses methods of preparation of copolymers of amino acids wherein polyamines are reacted with maleic acid and ammonia to form a polymer network. These materials are excellent inhibitors of metal scale deposition. U.S. Pat. Appl. Ser. No. 08/007,376 filed Jan. 21, 1993, by Louis L. Wood, incorporated herein by reference, discloses methods of preparation of polymers of amino acids wherein maleic acid and ammonia are reacted at high temperature to form a polymer network. These materials are excellent inhibitors of metal scale deposition. Summary of the Invention We have discovered that polyamino acids having a charge density of COO " approximately equal to 10 "3 mole/g of polymer, especially those based on the acidic amino acids, aspartic acid and glutamic acid, or copolymers of these acids such as those described in U.S. Pat. Application 07/926,242, filed August 7, 1992, by Louis L. Wood, incorporated herein by reference or those described in U.S. Pat. 3,846,380, incorporated herein by reference, or those described in U.S. Pat. Applic 07/994,922 filed December 22, 1992, by Louis L. Wood, incorporated herein by reference, or their salts, when mixed with citric acid or its salts, provide a mixture that has properties of calcium chelation significantly beyond that of the additive effects of the two compounds and is extremely useful in a detergent composition. Such compositions are especially valuable in softening water for detergent formulation and in prevention of scale formation where the calcium salts are problematic. One object of this invention is to provide a composition useful in inhibition or reduction of calcium scale formation in hard water, boiler water, cooling water, oil well waters, agricultural sprays, irrigation water, and laundry waters through its incorporation in formulations for treatment of such conditions. Another object is to provide a composition which inhibits or reduces the deposition of calcium salts in clothing during laundering when incorporated in a detergent. Another object is to prevent or reduce deposition of scale on glassware washed in an automatic dishwasher by addition of the composition to a dishwashing detergent. Yet another object is to prevent or reduce deposition of dental calculus on teeth or objects used in the oral cavity via incorporation in a suitable formulation. A final object is to provide methods for preventing or reducing calcium scale formation which are effective, low in cost, and environmentally benign. DEFINITIONS Polyaspartate includes the L and the D,L stereoisomers in any of the ratios present as well as the a and β amide bonds of the aspartate moiety. All percentages and ratios are by weight. The salts of polyamino acids and derivatives thereof include but are not limited to, the alkali and alkaline earth metals, examples of which as their cations are, Na + , K + , Mg + , Li + , and Ca + \ Zn ++ , Ba + \ Co ++ , Fe ++ , Fe ++t , and NH 4 \ The salts of citric acid include but are not limited to, the alkali and alkaline earth metals examples of which as their cations are, Na + , K + , Mg + , Li\ and Ca ++ , Zn ++ , Ba ++ , Co ++ , Fe ++ , Fe +++ , and NH 4 + . Detailed Description of the Embodiments. The uses of polyamino acids and their derivatives are well known in the prevention of the deposition of metal scale salts, thus providing excellent properties for prevention of such scale in evaporation or use of hard water, treatments for boiler water, cooling water, oil well waters, agricultural sprays and irrigation water. Further, this property makes them useful as builders in detergents, where deposition of metal salts are injurious to clothing and impart a hard crust to the textile fibers. Their use to prevent deposition of scale on glassware makes them desirable in detergents for automatic dishwashers and the like. Citrates are also well known to have similar properties and Wisk™, (a product of Lever Brothers, New York, NY), cites sodium citrate as the water softening agent on its label. Both polyamino acids and citrates have been used in water treatments and laundry detergents. It is well known that such materials can be used together, however, we have found that mixtures of citric acid and polyamino acids, in their acid or salt forms, or certain derivatives of polyamino acids do not chelate calcium as would be expected but that certain ratios of these materials are synergistic, thus providing benefits far beyond expectation in the chelation of calcium and thus the inhibition of calcium scale deposits or water softening. We have discovered a synergistic composition for sequestration of calcium ions comprised of (a) citric acid or its salts and Ob) a polyamino acid having a charge density of COO " approximately equal to 10 "3 mole/g of polymer in a ratio of from 75 to 25 of polymer to citrate to .1 to 99-9 of polymer to citrate. A preferred ratio of polymer or its salts to citric acid or its salts is between 1 to 1 and 1 to 99 which provides an enhanced chelation of Ca ++ . EXAMPLE 1 Oxalate Titration for Calcium Sequestration This procedure is well known in the art to demonstrate Ca ion sequestration. The sample, 0.25 g, was placed in 100 ml of deionized water and 1.0 ml of 3% sodium oxalate solution was added (in deionized water). The pH was adjusted to 9-0-9-2 with 10% NaOH or 10% HCl. The solution was titrated to the appearance of turbidity with 0.1 M CaCl 2 solution (in deionized water). The results of the assay using the ratios of polyamino acids or derivatives thereof to citrate indicated are given in Table 1. Additive 1 is the salt of polyaspartic acid or one of its copolymers, while Additive II is one of the salts of citrate or other commonly used detergent additives. The higher the amount of CaCl 2 consumed, the better the Ca sequestering ability of the additives. Table 1 Additive I (mg) 250 200 125 50 25 12.5 0 50 125 200 225 237.5 250 Additive II (mg) CaCl 2 Titrant Used (ml) polyaspartic acid a 7.5 9-35 9-55 10.45 9.75 8.35 sodium citrate polyaspartic acid a 7.5 7.15 6.2 7.3 8.0 s o d i u m tripolyphosphate polyaspartic acid a 7.5 7.65 7.8 6.75 6.25 sodiumnitrilot-riacetate DETA b, 7polyaspartic acid copolymer 7.15 7.75 9-2 9-6 10.6 9.15 8.35 sodium citrate DETA/polyaspartic acid copolymer 7.15 7.0 7.15 6.95 8.35 sodium EDTA c polyaspartic acid d 7.95 8.2 8.8 10.2 8.35 sodium citrate polyglutamic acid 6.35 7.2 8.2 8.9 9-0 8.35 sodium citrate polyglutamic acid 6.35 6.9 6.5 7.3 8.0 s o d i u m tripolyphosphate polyglutamic acid 6.35 6.3 6.25 sodiumnMotriacetate polyacrylate, 2000 mw 10.1 8.8 8.0 s o d i u m tripolyphosphate polyacrylate, 4500 mw 12.3 13-35 14.3 8.35 sodium citrate polyacrylate, 2000 mw 10.1 10.95 8.35 sodium άt-tate a prepared by method of U.S. Pat. Appl. Ser. No. 08/007,376 in which the salt is prepared by reacting maleic acid with ammonia in a ratio of 1:1, at a temperature of 190, for four hours or less and hydrolyzed with a metal hydroxide or ammonium hydroxide. b prepared by method of U.S. Pat. Appl. Ser. No. 07/926,242 in which the salt is prepare by reacting (1) maleic acid, (2) ammonia and (3) a polyamine at a temperature above 120° C. c DETA stands for diethylene triamine; EDTA stands for ethylenediamine tetraacetic acid d prepared by thermal polymerization of L-aspartic acid at 240° C Example 2. Synergism of citrate and the lysine copolymer of polyaspartic acid. The assay of Example 1 was used to evaluate a lysine copolymer of polyaspartic acid prepared by the method of U.S. Pat. Appl. Ser. No.07/926,242, filed August 6, 1992, by Louis L. Wood, incoφorated herein by reference, and compared with the polyaspartic made by the method of U.S. Pat. Appl. Ser. 08/007,376, filed Jan. 21, 1993, by Louis L. Wood, incoφorated herein by reference, in duplicate runs and the results are given in Table 2. Additive I is the salt of polyaspartic acid or one of its copolymers. Table 2 Additive I (%) 100 95 75 50 25 10 5 1 0.1 0 sodium citrate (%) 0 5 25 50 75 90 95 99 99.9 100 CaCl 2 Titrant Used (ml) Additive I polyaspartic acid a 7.4 7.3 8.6 8.7 11.0 11.2 10.7 9.8 8.6 8.8 polyaspartic acid a 7.4 7.7 8.7 8.5 10.9 11.7 10.9 10.2 9-3 9.2 lysine copolymer 8.4 9.5 10.1 11.2 11.5 - 10.8 8.5 8.8 of polyaspartic acid b lysine copolymer 8.6 9.3 9.8 11.0 11.5 - 9.9 9.2 9.2 of polyaspartic acid b a prepared by method of U.S. Pat. Appl. Ser. No. 08/007,376 as detailed in Example 1. b prepared by method of U.S. Pat. Appl. Ser. No. 07/926,242 as detailed in Example 1. It will be apparent to those skilled in the art that the examples and embodiments described herein are by way of illustration and not of limitation, and that other examples may be utilized without departing from the spirit and scope of the present invention, as set forth in the appended claims.

Claims: We claim: 1. A detergent composition comprising citric acid and a polymer, said polymer being selected from the group consisting of polyamino acids and polyamine copolymers of polyamino acids, in a ratio of from 75 to 25 of polymer to citrate to .1 to 99-9 of polymer to citrate. 2. The composition of claim 1 wherein the ratio of polymer to citrate is from 1 to 1 to 1 to 99- 3. The composition of claim 1 in which the polymer is polyaspartic acid. 4. The composition of claim 1 in which the polymer is polyglutamic acid. 5. The composition of claim 1 in which the polymer is composed of one or more amino acids. 6. The composition of claim 1 in which the polymer is prepared by reacting maleic acid, ammonia, and a polyamine. 7. The composition of claim 1 in which the polymer is prepared by reacting maleic acid and ammonia. 8. The composition of claim 1 in which the polymer is prepared by reacting maleic acid, ammonia, and an amino acid. 9. The composition of claim 6 in which the polyamine is diethylene triamine. 10. The composition of claim 8 in which the amino acid is lysine.

Inventors: CALTON GARY J, WOOD LOUIS L, CALTON, GARY, J., WOOD, LOUIS, L.
Applicants: BAYER AG
Application year: 1994
Main classification: C11D1
IPC codes: C02F5, C08G69, C08G73, C11D3, C11D7